US4415710A - Curable compositions, based on alkylene-alkyl acrylate copolymers, containing preformed, reactive organo titanate catalysts - Google Patents
Curable compositions, based on alkylene-alkyl acrylate copolymers, containing preformed, reactive organo titanate catalysts Download PDFInfo
- Publication number
- US4415710A US4415710A US06/334,673 US33467381A US4415710A US 4415710 A US4415710 A US 4415710A US 33467381 A US33467381 A US 33467381A US 4415710 A US4415710 A US 4415710A
- Authority
- US
- United States
- Prior art keywords
- composition
- carbon atoms
- formula
- alkylene
- diol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
Definitions
- This invention relates to preformed, reactive organo titanate catalysts which can be easily and readily dispersed throughout a resin matrix of an alkylene-alkyl acrylate copolymer to provide heat curable compositions having improved cure speeds.
- the compositions of this invention are particularly useful in extrusion applications, being capable of extrusion, without scorch, about electrical conductors such as electrical wires and cables providing coatings thereon characterized by improved surface characteristics.
- the present invention provides performed, reactive organo titanate catalysts which can be easily and readily dispersed throughout a resin matrix of an alkylene-alkyl acrylate copolymer and serve the dual function of crosslinking the alkylene-alkyl acrylate copolymer to a crosslinking product, while catalyzing the crosslinking reaction.
- the heat curable compositions of this invention comprising an alkylenealkyl acrylate copolymer and a preformed organo titanate catalyst, can be extruded, without scorch, about electrical wires and cables and cured at improved, i.e. faster, cure speeds providing protective coatings which, being free of voids and gel specks, are characterized by improved surface characteristics.
- the preformed, reactive organo titanate catalysts of this invention which range from liquids to solids at ambient temperatures and pressures, contain the repeating unit having the formula: ##STR1## wherein: R is a divalent hydrocarbon radical usually having a maximumn of 18 carbon atoms, generally having 3 to 18 carbon atoms, preferably having 3 to 12 carbon atoms; and each R 1 , which can be the same or different, is a monovalent hydrocarbon radical usually having a maximum of 18 carbon atoms, generally having 2 to 18 carbon atoms, preferably having 2 to 12 carbon atoms.
- suitable monovalent hydrocarbon radicals for R 1 are alkyl radicals generally having 2 to 18 carbon atoms, preferably having 2 to 12 carbon atoms such as ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, n-dodecyl and the like; aryl radicals having 6 to 8 carbon atoms such as phenyl, methylphenyl, ethylphenyl and the like; cycloaliphatic radicals having 5 to 8 carbon atoms such as cyclopentyl, cyclohexyl and the like.
- alkylene radicals generally having 3 to 12 carbon atoms, preferably having 3 to 8 carbon atoms such as propylene, butylene, hexylene, octylene and the like; alkoxy radicals generally having 2 to 12 carbon atoms, preferably having 2 to 6 carbon atoms such as methoxymethyl, methoxyethyl, ethoxyethyl, ethoxypropyl, propoxypropyl, propoxybutyl and the like.
- the preformed, reactive organo titanate catalysts are produced by reacting a mixture containing an organo titanate, a polyol, preferably a diol and a monohydric alcohol wherein the total (OH) functionality of the polyol and monohydric alcohol is substantially equal to the (OR) functionality of the organo titanate.
- reactive catalysts By varying the amount of monohydric alcohol reactant relative to the polyol reactant, preformed, reactive catalysts can be produced which range from liquids to solids. Increasing the amount of monohydric alcohol reactant decreases the melting point of the product as shown in the examples.
- the present invention allows for the tailoring of the reactive catalyst, from a solid to a liquid, as desired, to take advantage of the process equipment available for metering of the catalyst to and admixing the catalyst with, the alkylene-alkyl acrylate copolymers.
- organo titanates to be used in the preparation of the preformed, reactive organo titanates are compounds having the formula:
- each R 2 which can be the same or different, is a monovalent hydrocarbon radical, generally having 2 to 18 carbon atoms, preferably having 2 to 14 carbon atoms.
- suitable monovalent hydrocarbon radicals for R 2 are alkyl radicals such as ethyl, n-propyl, isopropyl, butyl, n-octyl, lauryl, myristyl, stearyl and the like; cycloaliphatic radicals such as cyclopentyl, cyclohexyl and the like; aryl radicals such as phenyl, methylphenyl, chlorophenyl and the like; alkaryl radicals such as benzyl and the like.
- Organo titanates falling within the scope of Formula II are known compounds and can be conveniently prepared as described in U.S. Pat. No. 2,984,641 to Leon E. Wolinsky patented May 16, 1961.
- Polyols suitable for purposes of this invention are compounds having at least two primary hydroxyl groups attached to non-adjacent carbon atoms and have the general formula HO-R-OH, wherein R is as previously defined.
- polystyrene resins such as the diols having the formula: ##STR2## wherein the sum of m+p is at least 2, preferably 2 to 20 inclusive and R' and R", which can be the same or different are hydrogen or alkyl and when alkyl, contain 1 to 20 carbon atoms.
- Specific compounds include, among others, propylene glycol, butanediol-1,4, hexanediol-1,6, decanediol-1,10, neopentyl glycol and the like.
- a has a value of at least 1, preferably 2 to 20, and x has a value of at least 2, preferably 2 to 10.
- di(ethylene glycol), di(propylene glycol) including the commercially available poly(ethylene glycol) and poly(propylene glycol).
- polystyrene resin examples include cycloaliphatic polyhydric alcohols such as cyclohexanedimethanol and the like, and other polyols which are described in U.S. application Ser. No. 106,502, now U.S. Pat. No. 4,351,926 filed Dec. 26, 1979 in the name of Michael J. Keogh and assigned to a common assignee, Union Carbide Corporation, the disclosure of which is incorporated herein by reference.
- the polyols can have substituents such as halogen and the like. Utilizing halogenated polyols in the preparation of the preformed, reactive organo titanate catalysts provides these catalysts with a built-in flame retardant capability which is manifested in the alkylene-alkyl acrylate compositions.
- Suitable monohydric alcohols which have the general formula R 1 -OH, are the following: ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, isoamyl alcohol, n-hexyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, benzyl alcohol and the like.
- Particularly desirable alcohols are the saturated, aliphatic primary alcohols having a maximum of 12 carbon atoms.
- R 1 is as previously defined.
- reaction of a mixture of an organo titanate, a monohydric alcohol and polyol, as described, can be carried out in any suitable vessel, as for example, a stirred autoclave and the like.
- the temperature at which the reaction is conducted is not critical and can range from about 25° C. to about 250° C., preferably from about 100° C. to about 200° C.
- the reaction can be carried out under atmospheric or subatmospheric pressure. Also, the reaction can be carried out in the presence of a solvent such as toluene, xylene, decalin and the like.
- a solvent such as toluene, xylene, decalin and the like.
- alkylene-alkyl acrylate copolymers which are admixed with the performed, reactive organo titanates, to form the compositions of this invention, are known copolymers produced by reacting an alkene with an alkyl acrylate.
- Suitable alkenes are ethylene, propylene, butene-1, isobutylene, pentene-1, 2-methylbutene-1, 3-methylbutene-1, hexene, heptene-1, octene-1 and the like; and mixtures thereof.
- the alkylene moiety of the alkylene-alkyl acrylate copolymer generally contains from 2 to 18 carbon atoms, preferably 2 to 3 carbon atoms.
- Suitable alkyl acrylate monomers which are copolymerized with the alkenes fall within the scope of the following formula: ##STR4## wherein R 1 is hydrogen or methyl and R 2 is alkyl having one to 8 carbon atoms.
- Illustrative compounds encompassed by this formula are: methyl acrylate, ethyl acrylate, t-butyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate and the like; and mixtures thereof.
- Alkylene-alkyl acrylate copolymers generally have a density (ASTMD-1505 with a conditioning as in ASTMD-147-72) of about 0.92 to about 0.94 and a melt index (ASTMD-1238 at 44 psi tested pressure) of about 0.5 to about 500 decigrams per minute.
- the preferred copolymer generally has about one to about 50 percent by weight combined alkyl acrylate, preferably about 5 to about 30 percent by weight combined alkyl acrylate.
- the amount of preformed, reactive organo titanate catalyst admixed with the alkylene-alkyl acrylate copolymers is sufficient to cure the copolymers to crosslinked products. Generally, this amount is on the order of about 0.1 to about 10 percent by weight based on the weight of the alkylene-alkyl acrylate copolymer.
- compositions of this invention may be added various additives, in amounts well known in the art, such as fillers among which can be mentioned carbon black, clay, talc, calcium silicate, calcium carbonate, silica, aluminum hydroxide and the like, antioxidants such as 1,2-dihydro-2,3,4-trimethylquinoline and the like.
- fillers among which can be mentioned carbon black, clay, talc, calcium silicate, calcium carbonate, silica, aluminum hydroxide and the like, antioxidants such as 1,2-dihydro-2,3,4-trimethylquinoline and the like.
- compositions can be rendered flame retardant by the addition thereto of halogen containing flame retardants such as decabromodiphenyloxide, ethylene(bis-tetra-bromophthalimide), chlorinated polyethylene, polyvinyl chloride and halogenated paraffin waxes, alone, or in admixture with organic or inorganic antimony compounds such as antimony oxide and/or alkaline earth metal oxides, carbonates, hydroxides and sulfates.
- organic or inorganic antimony compounds such as antimony oxide and/or alkaline earth metal oxides, carbonates, hydroxides and sulfates.
- alkaline earth metal compounds can be noted calcium oxide, calcium carbonate, calcium hydroxide, calcium sulfate, magnesium oxide, magnesium carbonate, magnesium hydroxide and magnesium sulfate; silane coupling agents and the like.
- mixtures of reactants and additives can be used in producing the preformed, reactive catalysts and in formulating the compositions if so desired.
- Formulation of the compositions of this invention can be carried out by mixing the components thereof in a suitable mixer such as a Brabender mixer, at elevated temperatures on the order of about 100° C. to about 130° C. until a blend is obtained, as for example, described in reference to the examples which follow.
- a suitable mixer such as a Brabender mixer
- the curing or crosslinking of the compositions is effected by heating the compositions at elevated temperatures on the order of about 180° C. to about 450° C., preferably temperatures on the order of about 230° C. to about 320° C.
- compositions of this invention were subjected to the Monsanto Rheometer test, which can be used to determine cure speed and the degree of cure or crosslinking.
- FIG. 1 of this patent shows the typical Monsanto Rheometer curve.
- the cure level (highest crosslink density) is designated as H. It is measured in terms of inch-pounds or torque on the Rheometer test equipment. A higher value for H corresponds to a higher crosslink density.
- the preparation of the preformed, reactive organo titanate catalysts was carried out by charging the reactants into a reaction flask, heating the contents of the flask to a maximum temperature of about 150° C. until cessation of volatiles (isopropyl alcohol) generated, at which point there was no further change in viscosity.
- the final stage of the reaction was conducted under vacuum for ease in recovering the alcohol by-product.
- compositions were admixed to a blend in a Brabender mixer, removed from the Brabender mixer and molded into plaques having dimensions of 3 inches by 8 inches by 0.075 inch, in a press, under the following conditions:
- compositions of this invention had a faster cure speed as compared to the Control.
- Example 3 The composition of Example 3 was extruded onto a copper wire and the coating on the wire cured under a nitrogen gas atmosphere at a temperature of 300° C. After the coating was cured and visually inspected, it was stripped off the wire and the stripped material was deformed into plaques, having dimensions of 3 inches by 8 inches by 0.075 inch, in a press under the following conditions:
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
Description
Ti(OR.sup.2).sub.4 Formula II
HO--C.sub.a H.sub.2a O).sub.x H Formula IV.
__________________________________________________________________________ MOLAR RATIOS Isopropyl Alcohol C.sub.12 OH.sup.1 CHDM.sup.2 TIPT.sup.3 Melting Point Recovered Theoretical __________________________________________________________________________ a (Control) -- 2.00 1.00 190° C. -- -- b 0.40 1.80 1.00 86° C. -- -- c 0.75 1.63 1.00 -- 72.1 72.1 d 1.00 1.50 1.00 68° C. 35.5 36 e 2.00 1.00 1.00 liquid 71.7 72 __________________________________________________________________________ .sup.1 dodecyl alcohol .sup.2 1,4cyclohexanedimethanol .sup.3 tetraisopropyl titanate
______________________________________ INITIAL FINAL ______________________________________ Pressure = 200 psi followed 5000 psi by Temperature = 130° C. 130° C. Time Cycle = 7minutes 3 minutes ______________________________________
______________________________________ GRAMS ______________________________________ EXAMPLE 1 Ethylene-ethyl acrylate copolymer composition 97 Preformed, reactant organo titanate catalyst (b) 3 EXAMPLE 2 Ethylene-ethyl acrylate copolymer composition 97 Preformed, reactive organo titanate catalyst (c) 3 EXAMPLE 3 Ethylene-ethyl acrylate copolymer composition 97 Preformed, reactive organo titanate catalyst (d) 3 EXAMPLE 4 Ethylene-ethyl acrylate copolymer composition 97 Preformed, reactive organo titanate catalyst (e) 3 CONTROL Ethylene-ethyl acrylate copolymer composition 97 Catalyst (a) 3 ______________________________________
______________________________________ PARTS BY WEIGHT ______________________________________ Ethylene-ethyl acrylate copolymer containing 15 56 percent by weight combined ethyl acrylate - Melt Index 1.3 Talc coated with zinc stearate 21.8 Antimony oxide 2.5 Calcium carbonate 2.5 Ethylene(bis-tetrabromophthalimide) 16.5 (flame retardant) 1,2-di-hydro-2,3,4-trimethylquinoline 0.6 (anti-oxidant) Vinyl-tris(2-methoxyethoxy)silane (coupling agent) 0.2 ______________________________________
Claims (17)
HO--C.sub.a H.sub.2a O.sub.x H
R.sup.1 --OH
Ti(OR.sup.2).sub.4
HO--R--OH
R.sup.1 --OH
Ti(OR.sup.2).sub.4
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/334,673 US4415710A (en) | 1981-12-28 | 1981-12-28 | Curable compositions, based on alkylene-alkyl acrylate copolymers, containing preformed, reactive organo titanate catalysts |
US06/518,428 US4524201A (en) | 1981-12-28 | 1983-08-02 | Reactive organo titanate catalysts |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/334,673 US4415710A (en) | 1981-12-28 | 1981-12-28 | Curable compositions, based on alkylene-alkyl acrylate copolymers, containing preformed, reactive organo titanate catalysts |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/518,428 Division US4524201A (en) | 1981-12-28 | 1983-08-02 | Reactive organo titanate catalysts |
Publications (1)
Publication Number | Publication Date |
---|---|
US4415710A true US4415710A (en) | 1983-11-15 |
Family
ID=23308268
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/334,673 Expired - Lifetime US4415710A (en) | 1981-12-28 | 1981-12-28 | Curable compositions, based on alkylene-alkyl acrylate copolymers, containing preformed, reactive organo titanate catalysts |
Country Status (1)
Country | Link |
---|---|
US (1) | US4415710A (en) |
Cited By (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6323288B1 (en) | 1993-07-13 | 2001-11-27 | Chevron Phillips Chemical Company Lp | Compositions having ethylenic backbone and benzylic, allylic, or ether-containing side-chains, oxygen scavenging compositions containing same, and process for making these compositions by esterification or transesterification of a polymer melt |
US6333087B1 (en) | 1998-08-27 | 2001-12-25 | Chevron Chemical Company Llc | Oxygen scavenging packaging |
US20020002238A1 (en) * | 2000-05-19 | 2002-01-03 | Raymond Laplante | Compatible blend systems of oxygen barrier polymers and oxygen scavenging polymers |
US6410807B1 (en) | 2000-05-10 | 2002-06-25 | Chevron Phillips Chemical Company Lp | Synthesis of cyclohexene dimethanol compounds |
US6437086B1 (en) | 2000-10-05 | 2002-08-20 | Chevron Phillips Chemical Company Lp | Non-extractable polymeric metal salt useful in catalyzing oxygen scavenging |
US6454965B1 (en) | 1999-03-24 | 2002-09-24 | Chevron Phillips Chemical Company Lp | Oxygen scavenging polymers in rigid polyethylene terephthalate beverage and food containers |
US6515067B2 (en) | 2001-01-16 | 2003-02-04 | Chevron Phillips Chemical Company Lp | Oxygen scavenging polymer emulsion suitable as a coating, an adhesive, or a sealant |
US6517776B1 (en) | 2000-11-03 | 2003-02-11 | Chevron Phillips Chemical Company Lp | UV oxygen scavenging initiation in angular preformed packaging articles |
US6525123B1 (en) | 2000-05-19 | 2003-02-25 | Chevron Phillips Chemical Company Lp | Compatible blend systems from ethylene vinyl alcohol and oxygen scavenging polymers |
US6527976B1 (en) | 2000-11-27 | 2003-03-04 | Chenron Phillips Chemical Company Lp | Epoxy-, melamine- and isocyanate cured oxygen scavenging compositions and methods of preparing the same |
US6559205B2 (en) | 2001-01-16 | 2003-05-06 | Chevron Phillips Chemical Company Lp | Oxygen scavenging polymer blends and emulsion-based methods for preparing same |
US6572783B1 (en) | 2000-11-27 | 2003-06-03 | Chevron Phillips Chemical Company Lp | Vinyl crosslinked oxygen scavenging compositions and methods of preparing the same |
US20030151025A1 (en) * | 2002-02-14 | 2003-08-14 | Hu Yang | Oxygen scavenging compositions comprising polymers derived from benzenedimethanol monomers |
US20030153644A1 (en) * | 2002-02-08 | 2003-08-14 | Hu Yang | Oxygen scavenging compositions comprising polymers derived from tetrahydrofurfuryl monomers |
US6607795B1 (en) | 2001-12-19 | 2003-08-19 | Chevron Phillips Chemical Company Lp | Oxygen scavenging compositions comprising polymers derived from aromatic difunctional monomers |
US6610215B1 (en) | 2000-10-16 | 2003-08-26 | Chevron Phillips Chemical Co., Lp | Oxygen scavenging compositions suitable for heat triggering |
US20030183801A1 (en) * | 2002-03-28 | 2003-10-02 | Hu Yang | Porous oxygen scavenging material |
US20030218152A1 (en) * | 2001-11-30 | 2003-11-27 | Hu Yang | Oxygen barrier copolymer |
US6664320B1 (en) | 2000-02-22 | 2003-12-16 | Chevron Phillips Chemical Company Lp | Using solventless metal oleate in making metal masterbatch |
US20030235669A1 (en) * | 2000-05-19 | 2003-12-25 | Hu Yang | Enhanced oxygen barrier performance from modification of vinyl alcohol polymers (PVOH) or ethylene vinyl alcohol copolymers (EVOH) |
US20030235708A1 (en) * | 1998-07-31 | 2003-12-25 | Hu Yang | Oxygen scavenging polymers as active barrier tie layers in multilayered structures |
US20040058178A1 (en) * | 2000-05-19 | 2004-03-25 | Chevron Phillips Chemical Company Lp. | Enhanced oxygen barrier performance from modification of ethylene vinyl alcohol copolymers (EVOH) |
US20040129554A1 (en) * | 2002-10-15 | 2004-07-08 | Solis James A. | Process for subjecting to actinic radiation and storing an oxygen scavenger, and a stored oxygen scavenger |
US6818150B2 (en) | 2000-12-22 | 2004-11-16 | Chevron Phillips Chemical Company Lp | UV- or heat-triggered low oxygen packaging system employing an oxidizable polymer resin and a peroxide |
US6852894B2 (en) | 1997-05-16 | 2005-02-08 | Chevron Phillips Chemical Company Lp | Tribenzoyl compounds |
US20050104033A1 (en) * | 2003-11-19 | 2005-05-19 | Schmidt Richard P. | Transition metal carboxylates as catalysts for oxygen scavenging |
US20050279967A1 (en) * | 2002-10-15 | 2005-12-22 | Richard Dayrit | Process for triggering, storing, and distributing an oxygen scavenger, and a stored oxygen scavenger |
US7056565B1 (en) | 1998-07-31 | 2006-06-06 | Chevron Phillips Chemical Company, Lp | Container having oxygen-scavenging core layer |
US20060276368A1 (en) * | 2005-06-07 | 2006-12-07 | Speer Drew V | Method of triggering a film containing an oxygen scavenger |
US7247390B1 (en) | 2000-05-19 | 2007-07-24 | Chevron Phillips Chemical Company, Lp | Compatible blend systems of oxygen barrier polymers and oxygen scavenging polymers |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2398350A (en) * | 1942-08-14 | 1946-04-16 | Nat Dairy Prod Corp | Method of producing elastic polymer |
US2412476A (en) * | 1945-10-25 | 1946-12-10 | Goodrich Co B F | Treatment of acrylic ester polymers |
US3491075A (en) * | 1965-10-13 | 1970-01-20 | Union Oil Co | Crosslinking of polymers having dependent ester groups with polyvalent metal alkoxides |
US3631161A (en) * | 1970-02-05 | 1971-12-28 | Union Carbide Corp | Method for crosslinking ethylene containing polymers |
US3904572A (en) * | 1972-04-20 | 1975-09-09 | Mitsubishi Gas Chemical Co | Cold-setting coating composition based on hydroxy-containing vinyl polymer |
US4005247A (en) * | 1975-10-30 | 1977-01-25 | Ashland Oil, Inc. | Pressure sensitive adhesive compositions |
US4012567A (en) * | 1975-03-12 | 1977-03-15 | Uniroyal Inc. | Titanate ester cure of unsaturated elastomers |
US4020214A (en) * | 1973-06-21 | 1977-04-26 | General Electric Company | Method of making an insulated electrical conductor using pressureless curing of filled ethylene containing polymeric compositions, and an insulated conductor formed thereby |
US4042766A (en) * | 1975-03-18 | 1977-08-16 | Sumitomo Chemical Company, Limited | Method for preparation of ionically crosslinked ethylene copolymers |
US4182811A (en) * | 1973-07-24 | 1980-01-08 | Bocharov Jury N | Polymeric gel catalyst for polymerization of α-olefines, conjugated and non-conjugated dienes |
US4185051A (en) * | 1977-12-22 | 1980-01-22 | Monsanto Company | Pressure sensitive adhesive compositions containing a polymetaloxane |
-
1981
- 1981-12-28 US US06/334,673 patent/US4415710A/en not_active Expired - Lifetime
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2398350A (en) * | 1942-08-14 | 1946-04-16 | Nat Dairy Prod Corp | Method of producing elastic polymer |
US2412476A (en) * | 1945-10-25 | 1946-12-10 | Goodrich Co B F | Treatment of acrylic ester polymers |
US3491075A (en) * | 1965-10-13 | 1970-01-20 | Union Oil Co | Crosslinking of polymers having dependent ester groups with polyvalent metal alkoxides |
US3631161A (en) * | 1970-02-05 | 1971-12-28 | Union Carbide Corp | Method for crosslinking ethylene containing polymers |
US3904572A (en) * | 1972-04-20 | 1975-09-09 | Mitsubishi Gas Chemical Co | Cold-setting coating composition based on hydroxy-containing vinyl polymer |
US4020214A (en) * | 1973-06-21 | 1977-04-26 | General Electric Company | Method of making an insulated electrical conductor using pressureless curing of filled ethylene containing polymeric compositions, and an insulated conductor formed thereby |
US4182811A (en) * | 1973-07-24 | 1980-01-08 | Bocharov Jury N | Polymeric gel catalyst for polymerization of α-olefines, conjugated and non-conjugated dienes |
US4012567A (en) * | 1975-03-12 | 1977-03-15 | Uniroyal Inc. | Titanate ester cure of unsaturated elastomers |
US4042766A (en) * | 1975-03-18 | 1977-08-16 | Sumitomo Chemical Company, Limited | Method for preparation of ionically crosslinked ethylene copolymers |
US4005247A (en) * | 1975-10-30 | 1977-01-25 | Ashland Oil, Inc. | Pressure sensitive adhesive compositions |
US4185051A (en) * | 1977-12-22 | 1980-01-22 | Monsanto Company | Pressure sensitive adhesive compositions containing a polymetaloxane |
Cited By (52)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6323288B1 (en) | 1993-07-13 | 2001-11-27 | Chevron Phillips Chemical Company Lp | Compositions having ethylenic backbone and benzylic, allylic, or ether-containing side-chains, oxygen scavenging compositions containing same, and process for making these compositions by esterification or transesterification of a polymer melt |
US20030109643A1 (en) * | 1993-07-13 | 2003-06-12 | Ta Y. Ching | Compositions having ethylenic backbone and benzylic, allylic, or ether-containing side-chains, oxygen scavenging compositions containing same, and process for making these compositions by esterification or transesterification of a polymer melt |
US6906146B2 (en) | 1993-07-13 | 2005-06-14 | Phillips Petroleum Company | Compositions having ethylenic backbone and benzylic, allylic, or ether-containing side-chains, oxygen scavenging compositions containing same, and process for making these compositions by esterification or transesterification of a polymer melt |
US6852894B2 (en) | 1997-05-16 | 2005-02-08 | Chevron Phillips Chemical Company Lp | Tribenzoyl compounds |
US7056565B1 (en) | 1998-07-31 | 2006-06-06 | Chevron Phillips Chemical Company, Lp | Container having oxygen-scavenging core layer |
US7097890B1 (en) | 1998-07-31 | 2006-08-29 | Chevron Phillips Chemical Co. Lp | Polymer with pendent cyclic olefinic functions for oxygen scavenging packaging |
US6946175B2 (en) | 1998-07-31 | 2005-09-20 | Chevron Phillips Chemical Co., Lp | Oxygen scavenging polymers as active barrier tie layers in multilayered structures |
US20030235708A1 (en) * | 1998-07-31 | 2003-12-25 | Hu Yang | Oxygen scavenging polymers as active barrier tie layers in multilayered structures |
US20030152727A1 (en) * | 1998-08-27 | 2003-08-14 | Chevron Chemical Company Llc | Oxygen scavenging packaging |
US6406644B2 (en) | 1998-08-27 | 2002-06-18 | Chevron Phillips Chemical Company Lp | Oxygen scavenging packaging |
US7794804B2 (en) | 1998-08-27 | 2010-09-14 | Cryovac, Inc. | Oxygen scavenging packaging |
US6569506B1 (en) | 1998-08-27 | 2003-05-27 | Chevron Chemical Company Llc | Oxygen scavenging packaging |
US6333087B1 (en) | 1998-08-27 | 2001-12-25 | Chevron Chemical Company Llc | Oxygen scavenging packaging |
US6454965B1 (en) | 1999-03-24 | 2002-09-24 | Chevron Phillips Chemical Company Lp | Oxygen scavenging polymers in rigid polyethylene terephthalate beverage and food containers |
US20030012896A1 (en) * | 1999-03-24 | 2003-01-16 | Chevron Phillips Chemical Company Lp | Oxygen scavenging polymers in rigid polyethylene terephthalate beverage and food containers |
US6664320B1 (en) | 2000-02-22 | 2003-12-16 | Chevron Phillips Chemical Company Lp | Using solventless metal oleate in making metal masterbatch |
US6410807B1 (en) | 2000-05-10 | 2002-06-25 | Chevron Phillips Chemical Company Lp | Synthesis of cyclohexene dimethanol compounds |
US7026417B2 (en) | 2000-05-19 | 2006-04-11 | Chevron Phillips Chemical Co., Lp | Enhanced oxygen barrier performance from modification of vinyl alcohol polymers (PVOH) or ethylene vinyl alcohol copolymers (EVOH) |
US20040058178A1 (en) * | 2000-05-19 | 2004-03-25 | Chevron Phillips Chemical Company Lp. | Enhanced oxygen barrier performance from modification of ethylene vinyl alcohol copolymers (EVOH) |
US20020002238A1 (en) * | 2000-05-19 | 2002-01-03 | Raymond Laplante | Compatible blend systems of oxygen barrier polymers and oxygen scavenging polymers |
US7288593B2 (en) | 2000-05-19 | 2007-10-30 | Cryovac, Inc. | Enhanced oxygen barrier performance from modification of ethylene vinyl alcohol copolymers (EVOH) |
US7247390B1 (en) | 2000-05-19 | 2007-07-24 | Chevron Phillips Chemical Company, Lp | Compatible blend systems of oxygen barrier polymers and oxygen scavenging polymers |
US7186464B2 (en) | 2000-05-19 | 2007-03-06 | Chevron Phillips Chemical Co. Lp | Compatible blend systems of oxygen barrier polymers and oxygen scavenging polymers |
US7087277B2 (en) | 2000-05-19 | 2006-08-08 | Chevron Phillips Chemical Company Lp | Enhanced oxygen barrier performance from modification of ethylene vinyl alcohol copolymers (EVOH) |
US20030235669A1 (en) * | 2000-05-19 | 2003-12-25 | Hu Yang | Enhanced oxygen barrier performance from modification of vinyl alcohol polymers (PVOH) or ethylene vinyl alcohol copolymers (EVOH) |
US6525123B1 (en) | 2000-05-19 | 2003-02-25 | Chevron Phillips Chemical Company Lp | Compatible blend systems from ethylene vinyl alcohol and oxygen scavenging polymers |
US6437086B1 (en) | 2000-10-05 | 2002-08-20 | Chevron Phillips Chemical Company Lp | Non-extractable polymeric metal salt useful in catalyzing oxygen scavenging |
US6610215B1 (en) | 2000-10-16 | 2003-08-26 | Chevron Phillips Chemical Co., Lp | Oxygen scavenging compositions suitable for heat triggering |
US6517776B1 (en) | 2000-11-03 | 2003-02-11 | Chevron Phillips Chemical Company Lp | UV oxygen scavenging initiation in angular preformed packaging articles |
US6527976B1 (en) | 2000-11-27 | 2003-03-04 | Chenron Phillips Chemical Company Lp | Epoxy-, melamine- and isocyanate cured oxygen scavenging compositions and methods of preparing the same |
US6572783B1 (en) | 2000-11-27 | 2003-06-03 | Chevron Phillips Chemical Company Lp | Vinyl crosslinked oxygen scavenging compositions and methods of preparing the same |
US6818150B2 (en) | 2000-12-22 | 2004-11-16 | Chevron Phillips Chemical Company Lp | UV- or heat-triggered low oxygen packaging system employing an oxidizable polymer resin and a peroxide |
US20050092963A1 (en) * | 2000-12-22 | 2005-05-05 | Chevron Phillips Chemical Company, Lp | UV-or heat triggered low oxygen packaging system employing an oxidizable polymer resin and a peroxide |
US7468144B2 (en) | 2000-12-22 | 2008-12-23 | Cryovac, Inc. | UV- or heat triggered low oxygen packaging system employing an oxidizable polymer resin and a peroxide |
US6559205B2 (en) | 2001-01-16 | 2003-05-06 | Chevron Phillips Chemical Company Lp | Oxygen scavenging polymer blends and emulsion-based methods for preparing same |
US6515067B2 (en) | 2001-01-16 | 2003-02-04 | Chevron Phillips Chemical Company Lp | Oxygen scavenging polymer emulsion suitable as a coating, an adhesive, or a sealant |
US6818151B2 (en) | 2001-11-30 | 2004-11-16 | Chevron Phillips Chemical Company Lp | Oxygen barrier copolymer |
US20030218152A1 (en) * | 2001-11-30 | 2003-11-27 | Hu Yang | Oxygen barrier copolymer |
US6607795B1 (en) | 2001-12-19 | 2003-08-19 | Chevron Phillips Chemical Company Lp | Oxygen scavenging compositions comprising polymers derived from aromatic difunctional monomers |
US20030153644A1 (en) * | 2002-02-08 | 2003-08-14 | Hu Yang | Oxygen scavenging compositions comprising polymers derived from tetrahydrofurfuryl monomers |
US6746622B2 (en) | 2002-02-08 | 2004-06-08 | Chevron Phillips Chemical Company Lp | Oxygen scavenging compositions comprising polymers derived from tetrahydrofurfuryl monomers |
US7022258B2 (en) | 2002-02-14 | 2006-04-04 | Chevron Phillips Chemical Company, Lp | Oxygen scavenging compositions comprising polymers derived from benzenedimethanol monomers |
US20030151025A1 (en) * | 2002-02-14 | 2003-08-14 | Hu Yang | Oxygen scavenging compositions comprising polymers derived from benzenedimethanol monomers |
US20030183801A1 (en) * | 2002-03-28 | 2003-10-02 | Hu Yang | Porous oxygen scavenging material |
US20050279967A1 (en) * | 2002-10-15 | 2005-12-22 | Richard Dayrit | Process for triggering, storing, and distributing an oxygen scavenger, and a stored oxygen scavenger |
US7494605B2 (en) | 2002-10-15 | 2009-02-24 | Cryovac, Inc. | Process for triggering, storing, and distributing an oxygen scavenger, and a stored oxygen scavenger |
US7238300B2 (en) | 2002-10-15 | 2007-07-03 | Solis James A | Process for subjecting to actinic radiation and storing an oxygen scavenger, and a stored oxygen scavenger |
US20040129554A1 (en) * | 2002-10-15 | 2004-07-08 | Solis James A. | Process for subjecting to actinic radiation and storing an oxygen scavenger, and a stored oxygen scavenger |
US20050104033A1 (en) * | 2003-11-19 | 2005-05-19 | Schmidt Richard P. | Transition metal carboxylates as catalysts for oxygen scavenging |
US7052628B2 (en) | 2003-11-19 | 2006-05-30 | Chevron Phillips Chemical Company, Lp | Transition metal carboxylates as catalysts for oxygen scavenging |
US20060276368A1 (en) * | 2005-06-07 | 2006-12-07 | Speer Drew V | Method of triggering a film containing an oxygen scavenger |
US7504045B2 (en) | 2005-06-07 | 2009-03-17 | Cryovac, Inc. | Method of triggering a film containing an oxygen scavenger |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4524201A (en) | Reactive organo titanate catalysts | |
US4415710A (en) | Curable compositions, based on alkylene-alkyl acrylate copolymers, containing preformed, reactive organo titanate catalysts | |
US4446279A (en) | Compositions based on a polysiloxane and an organo titanate and the use thereof in the preparation of water curable, silane modified alkylene-alkyl acrylate copolymers | |
US4526930A (en) | Production of water-curable, silane modified thermoplastic polymers | |
US4593071A (en) | Water-curable, silane modified ethylene polymers | |
CA1128232A (en) | Melt processable blend of non-silicone polymer and monoorgano polysiloxane resin | |
US4353997A (en) | Compositions based on water-curable, silane modified copolymers of alkylene-alkyl acrylates | |
US4753993A (en) | Compositions based on thermoplastic polymers and metal carboxylate silanol condensation catalysts | |
US4408011A (en) | Polysiloxanes and the use thereof in the production of silane modified alkylene-alkyl acrylate copolymers | |
EP0073027A2 (en) | Masterbatch composition comprising a matrix having a polysiloxane dispersed therein and a method for the preparation thereof | |
EP0004752B1 (en) | A water curable silane modified alkylene alkylacrylate copolymer, a process for its production and products made therefrom | |
JPH08261389A (en) | Flame-retardant heat-insulating composition having improved curing characteristic | |
US4707520A (en) | Composition based on water-curable thermoplastic polymers and metal carboxylate silanol condensation catalysts | |
PT92058A (en) | PROCESS FOR THE PREPARATION OF A COMPOSITION OF SILICONE COPOLYMERS WITH WATER, CONTAINING CHARGES AND ARTICLES BASED ON THAT COMPOSITION | |
US4440907A (en) | Process of producing a water-curable, silane modified alkylene-alkyl acrylate copolymer by reacting an alkylene-alkyl acrylate copolymer with a polysiloxane predispersed in a thermoplastic resin matrix | |
EP1457523B1 (en) | Flame-retardant resin composition free from halogen | |
US4598116A (en) | Scorch resistant compositions based on water-curable thermoplastic polymers having hydrolyzable, pendant silane moieties, and organo titanates | |
EP0353010B1 (en) | Self-extinguishing polymer composition | |
US4374958A (en) | Crosslinkable compositions based on alkylene-alkyl acrylate copolymers containing a polyol, an organo titanate and a molecular sieve | |
US4593072A (en) | Relatively water-stable compositions based on thermoplastic polymers containing pendant silane moieties | |
CA1242835A (en) | Water curable, azide sulfonyl silane modified, alkylene-alkyl acrylate copolymers | |
CA1177195A (en) | Compositions based on water-curable silane modified copolymers of alkylene-alkyl acrylates | |
CA1162343A (en) | Polymeric compositions | |
JPS6218577B2 (en) | ||
CA1186437A (en) | Production of silane modified copolymers of alkylene- alkyl acrylates, polysiloxanes having combined therein organo titanates and the use thereof in the production of silane modified copolymers of alkylene- alkyl acrylates |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: UNION CARBIDE CORPORATION, OLD RIDGEBURY ROAD, DAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:BARNABEO, AUSTIN E.;KEOGH, MICHAEL J.;REEL/FRAME:004001/0874 Effective date: 19820301 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
CC | Certificate of correction | ||
AS | Assignment |
Owner name: MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MOR Free format text: MORTGAGE;ASSIGNORS:UNION CARBIDE CORPORATION, A CORP.,;STP CORPORATION, A CORP. OF DE.,;UNION CARBIDE AGRICULTURAL PRODUCTS CO., INC., A CORP. OF PA.,;AND OTHERS;REEL/FRAME:004547/0001 Effective date: 19860106 |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
AS | Assignment |
Owner name: UNION CARBIDE CORPORATION, Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:MORGAN BANK (DELAWARE) AS COLLATERAL AGENT;REEL/FRAME:004665/0131 Effective date: 19860925 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M170); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M171); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 8 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M185); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 12 |